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Elucidation of the intrinsic catalytic principle of iron carbides remains a substantial challenge in iron-catalyzed Fischer-Tropsch synthesis (FTS), due to possible interference from other Fe-containing species. Here, we propose a facile approach to synthesize single-phase θ-Fe3C via the pyrolysis of a molecularly defined Fe-C complex (Fe4[Fe(CN)6]3), thus affording close examination of its catalytic behavior during FTS. The crystal structure of prepared θ-Fe3C is unambiguously verified by combined XRD and MES measurement, demonstrating its single-phase nature. Strikingly, single-phase θ-Fe3C exhibited excellent selectivity to light olefins (77.8%) in the C2-C4 hydrocarbons with less than 10% CO2 formation in typical FTS conditions. This strategy further succeeds with promotion of Mn, evident for its wide-ranging compatibility for the promising industrial development of catalysts. This work offers a facile approach for oriented preparation of single-phase θ-Fe3C and provides an in-depth understanding of its intrinsic catalytic performance in FTS. [ABSTRACT FROM AUTHOR]

Hydrogen storage by means of catalytic hydrogenation of suitable organic substrates helps to elevate the volumetric density of hydrogen energy. In this regard, utilizing cheaper industrial crude hydrogen to fulfill the goal of hydrogen storage would show economic attraction. However, because CO impurities in crude hydrogen can easily deactivate metal active sites even in trace amounts such a process has not yet been realized. Here, we develop a robust RuNi/TiO2 catalyst that enables the efficient hydrogenation of toluene to methyl-cyclohexane under simulated crude hydrogen feeds with 1000–5000 ppm CO impurity at around 180 °C under atmospheric pressure. We show that the co-localization of Ru and Ni species during reduction facilitated the formation of tightly coupled metallic Ru-Ni clusters. During the catalytic hydrogenation process, due to the distinct bonding properties, Ru and Ni served as the active sites for CO methanation and toluene hydrogenation respectively. Our work provides fresh insight into the effective utilization and purification of crude hydrogen for the future hydrogen economy. Efficient storage of crude hydrogen, through toluene hydrogenation to methylcyclohexane, is often inhibited by CO impurities. Here, the authors develop a RuNi/TiO2 catalyst which avoids deactivation through promoting simultaneous CO methanation. [ABSTRACT FROM AUTHOR]

Polyethylene terephthalate (PET) and CO2, two chemical wastes that urgently need to be transformed in the environment, are converted simultaneously in a one‐pot catalytic process through the synergistic coupling of three reactions: CO2 hydrogenation, PET methanolysis and dimethyl terephthalate (DMT) hydrogenation. More interestingly, the chemical equilibria of both reactions were shifted forward due to a revealed dual‐promotion effect, leading to significantly enhanced PET depolymerization. The overall methanol yield from CO2 hydrogenation exceeded the original thermodynamic equilibrium limit since the methanol was in situ consumed in the PET methanolysis. The degradation of PET by a stoichiometric ratio of methanol was significantly enhanced because the primary product, DMT was hydrogenated to dimethyl cyclohexanedicarboxylate (DMCD) or p‐xylene (PX). This synergistic catalytic process provides an effective way to simultaneously recycle two wastes, polyesters and CO2, for producing high‐value chemicals. [ABSTRACT FROM AUTHOR]

Deuterium (D) labeling is of great value in organic synthesis, pharmaceutical industry, and materials science. However, the state‐of‐the‐art deuteration methods generally require noble metal catalysts, expensive deuterium sources, or harsh reaction conditions. Herein, noble metal‐free and ultrathin ZnIn2S4 (ZIS) is reported as an effective photocatalyst for visible light‐driven reductive deuteration of carbonyls to produce deuterated alcohols using heavy water (D2O) as the sole deuterium source. Defective two‐dimensional ZIS nanosheets (D‐ZIS) are prepared in a surfactant assisted bottom‐up route exhibited much enhanced performance than the pristine ZIS counterpart. A systematic study is carried out to elucidate the contributing factors and it is found that the in situ surfactant modification enabled D‐ZIS to expose more defect sites for charge carrier separation and active D‐species generation, as well as high specific surface area, all of which are beneficial for the desirable deuteration reaction. This work highlights the great potential in developing low‐cost semiconductor‐based photocatalysts for organic deuteration in D2O, circumventing expensive deuterium reagents and harsh conditions. [ABSTRACT FROM AUTHOR]